Improved Shading Process

ABSTRACT

The present invention relates to new compounds, which are molecular combinations of a phthalocyanine and a mono-azo dyestuff linked via specific linking groups and to a process for their preparation. Further aspects are shading compositions using these compounds.

The present invention relates to new compounds, which are molecularcombinations of a phthalocyanine and a mono-azo dyestuff linked viaspecific linking groups and to a process for their preparation. Furtheraspects are an improved shading process for textile materials and alsoshading compositions using these compounds.

A frequently employed method in bleaching and whitening is to use violetor blue dyes concurrently in order to improve the bleaching andwhitening effect. If such a dye is used in conjunction with afluorescent whitening agent, this can serve two different purposes. Onone hand, it is possible to achieve an increase in the degree ofwhiteness by compensating for the yellowness of the fabric, in whichcase the white shade produced by the fluorescent whitening agent on thefabric is largely retained. On the other hand, the object can be toeffect with the dye in question a change in the shade of the whiteeffect produced by the fluorescent whitening agent on the fabric. It isthus possible to adjust the desired shade of the white effect.

Shading processes of materials such as paper and textile fabrics areknown from e.g. DE 3125495.

These disclosed shading processes use a physical mixture of aphotocatalyst and a dyestuff, which are not suitable for a regular usein detergent or softener formulations, because the dyestuffs accumulatewith every use and after a few uses the fabrics are colored.

Additionally, the use of a mixture of two components always requires theproper ratio of the two components.

To overcome the problem of accumulation WO 2006/024612 suggests amolecular combination of a photocatalyst and a dyestuff. A wide varietyof photocatalysts and classes of dyestuffs are disclosed. The specificcombinations disclosed in WO 2006/024612, however, have still thedisadvantage that a significant accumulation occurs and the dyeconjugate is not photo degraded rapidly enough.

Surprisingly it has now been found that when the phthalocyanine is asulfonated phthalo-cyanine and the dyestuff bonded thereto is a mono-azodyestuff linked via a specific linking group, photo degradation becomesrapid enough so that no color formation on the treated fabric occurs,even after repeated treatment. The improved shading process using thesecompounds has also an improved exhaustion onto the fabrics. The newcompounds are also highly efficient photocatalysts by additional lightabsorption and energy transfer to the phthalocyanine part of themolecule.

One aspect of the invention is a Zn—, Ca—, Mg—, Na—, K—, Al, Si—, Ti—,Ge—, Ga—, Zr—, In— or Sn—phthalocyanine compound of formula (1)(PC)-L-(D) (1) to which at least one mono-azo dyestuff is attachedthrough a covalent bonding via a linking group L wherein

-   PC is the metal-containing phthalocyanine ring system;-   D is the radical of a mono-azo dyestuff; and-   L is a group

wherein

-   -   R₂₀ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy or halogen;    -   R₂₁ is independently D, hydrogen, OH, Cl or F, with the proviso        that at least one is D;    -   R₁₀₀ is C₁-C₈alkylene    -   * is the point of attachment of PC;    -   # is the point of attachment of the dye.

In a specific embodiment the invention is a Zn—, Ca—, Mg—, Na—, K—, Al,Si—, Ti—, Ge—, Ga—, Zr—, In— or Sn— phthalocyanine compound of formula(1) (PC)-L-(D) (1) to which at least one mono-azo dyestuff is attachedthrough a covalent bonding via a linking group L wherein

-   PC is the metal-containing phthalocyanine ring system;-   D is the radical of a mono-azo dyestuff; and-   L is a group

wherein

-   -   R₂₀ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy or halogen;    -   R₂₁ is independently D, hydrogen, OH, Cl or F, with the proviso        that at least one is D;    -   * is the point of attachment of PC;    -   # is the point of attachment of the dye.

-   C₁-C₈alkyl is linear or branched alkyl, for example methyl, ethyl,    propyl, butyl, pentyl, hexyl, heptyl, octyl or isopropyl.

-   C₁-C₈alkoxy is linear or branched, for example methoxy, propoxy or    octoxy.

-   Halogen is F, Cl, Br or I, preferably Cl.

-   C₁-C₈alkylene is, for example, linear or branched methylene,    ethylene, propylene, butylene or pentylene.

For example the compound of formula 1 is of formula (1a)

in which

-   PC is the metal-containing phthalocyanine ring system,-   Me is Zn; Ca; Mg; Na; K; Al—Z₁; Si(IV)-(Z₁)₂; Ti(IV)-(Z₁)₂;    Ge(IV)-(Z₁)₂; Ga(III)-Z₁; Zr(IV)-(Z₁)₂; In(III)-Z₁ or Sn(IV)-(Z₁)₂-   Z₁ is an alkanolate ion; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆    ⁻; R₀SO₃; SO₄ ²⁻; NO₃ ⁻;-   F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion or oxalate ion, wherein    R₀ is hydrogen; or unsubstituted C₁-C₁₈alkyl;-   r is 0; 1; 2; 3 or 4;-   r′ is 1; 2; 3 or 4;-   each Q₂ is independently of each other —SO₃ ⁻M⁺ or a group    —(CH₂)_(m)—COO⁻M⁺; wherein M⁺ is H⁺, an alkali metal ion or the    ammonium ion and m is 0 or a number from 1 to 12;-   each Q′ is independently from each other a moiety of formula -L-D    wherein-   D is the radical of a mono-azo dyestuff; and-   L is a group

wherein

-   -   R₂₀ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy or halogen;    -   R₂₁ is independently D, hydrogen, OH, Cl or F, with the proviso        that at least one is D;    -   R₁₀₀ is C₁-C₈alkylene    -   * is the point of attachment of PC, # is the point of attachment        to D.

Preferably L is a group

Preferably, the sum of r and r′ is from 2 to 6, more preferably the sumis from 2 to 4.

Preferably, Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ hasthe meanings as defined above.

More preferably, Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, whereinZ₁ is chlorine, fluorine, bromine or hydroxyl. Particular preference isgiven to Zn.

In a preferred embodiment of the invention the compound of formula (1)is of formula (2a)

-   wherein-   Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ is    chloride, fluorine, bromine or hydroxyl;-   each Q₂ is independently from each other —SO₃ ⁻M⁺ or a group    —(CH₂)_(m)—COO⁻M⁺; wherein M⁺ is H⁺, an alkali metal ion or the    ammonium ion and m is 0 or a number from 1 to 12;-   D is the radical of a dyestuff;-   L is a group

wherein

-   -   R₂₁ is independently D, hydrogen, OH, Cl or F with the proviso        that at least one is D;    -   * is the point of attachment of PC,    -   # is the point of attachment to D;

-   r₂ is 0 or 1,

-   r₃ is 0 or 1, and

-   r₄ is 0 or 1.

For example each D is independently from each other a dyestuff radicalof formulae Xa, Xb, Xc or Xd

wherein

-   # marks the bond to the bridging group L,-   R_(α) is hydrogen; linear or branched, unsubstituted C₁-C₄-alkyl;    linear or branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; unsubstituted aryl or aryl, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl,-   Z₂, Z₃, Z₄, Z₅ and Z₆ are independently from each other hydrogen;    linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched    C₁-C₄-alkyl, which is substituted by at least one substituent chosen    from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear    or branched, unsubstituted C₁-C₄-alkoxy or linear or branched,    C₁-C₄-alkoxy, which is substituted by at least one substituent    chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,    carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and    pyridyl; halogen; OH; SO₂CH₂CH₂SO₃H; NO₂; COOH; COOC₁-C₄alkyl; NH₂;    NHC₁-C₄alkyl, wherein the alkyl group may be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN or COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, wherein the alkyl    groups may independently of each other be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl, wherein the aryl is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy; NHCOC₁-C₄alkyl or    NHCOOC₁-C₄alkyl,-   G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted    C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and    C₁-C₄alkyl; or —CO-arylene,-   n is 0; 1; 2 or 3,-   n′ is 0; 1 or 2,-   each M is independently from each other hydrogen; an alkali metal    ion or an ammonium ion.

The substituents in the naphthyl groups, when not attached to anindividual carbon atom can be attached in either ring of the naphthylradical. This is expressed by the horizontal line going through bothrings in, for example, in structural formula Xa, Xb and Xc.

For example C₁-C₄alkylene is methylene, ethylene, propylene or butylene.

Arylene in the context of the instant invention means phenylene ornaphthylene, preferably phenylene.

Preferably each D is independently from each other a dyestuff radical offormulae XIa, XIb, XIc or XId

wherein

-   # marks the bond to the bridging group L,-   Z₂ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl or OH,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl or    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, O₁—C₂alkoxy and    C₁-C₂alkyl,-   n is 0, 1, 2 or 3,-   n′ is 0, 1 or 2,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   # marks the bond to the bridging group L,-   Z₂ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl or OH,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl or    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 0, 1; 2 or 3,-   n′ is 0, 1 or 2,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   # marks the bond to the bridging group L,-   Z₂ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; NO₂,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, O₁—C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, O₁—C₂alkoxy and    C₁-C₂alkyl,-   n is 0, 1; 2 or 3,-   n′ is 0, 1 or 2,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   # marks the bond to the bridging group L,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂,-   Z₄ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; SO₂CH₂CH₂SO₃H; or NO₂,-   Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH;    NHCOC_(t)—C₂alkyl or NHCOOC_(t)—C₂alkyl,-   Z₆ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; or NO₂,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 0, 1; 2 or 3,-   n′ is 0, 1 or 2,-   each M is independently from each other hydrogen; Na⁺ or K.

Particularly preferred phthalocyanine compounds have the formula (3a),

in which

-   PC, L and D are as defined above (including the preferences),-   Me is Zn or Al—Z₁, Z₁ is chlorine, fluorine, bromine or hydroxyl;-   Y₃′ is hydrogen; an alkali metal ion or ammonium ion, and-   r is any number from 0 to 4, preferably any number from 1 to 4,-   r′ is any number from 1 to 4.

Particularly suitable individual dyestuff radicals D are of formulae 10,11, 12, 13 or 14

wherein # marks the bond to the bridging group L.

The sulfonic acid groups of the dyes represented by —SO₃H may also be inthe form of their salts, in particular of alkali metal salts, such asNa, K or Li salts or as ammonium salts. Also mixtures of the free acidand the corresponding salts are embraced.

A particularly suitable individual phthalocyanine is represented by thefollowing formula wherein the degree of sulfonation is between 2 and 3in the phthalocyanine ring.

Depending on the pH value of the medium the sulfonic acid groups of thephthalocynine ring as well as of the dyestuff groups may be more or lessdissociated.

A further embodiment of the present invention relates to a process forproducing compounds of formula (Ia)

wherein X and X′ is a leaving group andall other substituents have the meaning as defined above, including allpreferences and definitions.

For the synthesis of metal phthalocyanines, two different pathways maybe followed: either the initial synthesis of a metal-free phthalocyaninederivative and subsequent complexation with a metal salt or thesynthesis of a phthalocyanine ring system from a simple benzenoidprecursor by concomitant incorporation of the metal ion.

Substituents can be introduced before or after the formation of thephthalocyanine ring system. In the former case, this leads toderivatives with substituents in all four rings, whereas in the lattercase the degree of substitution will be variable.

By an introduction of suitable substituents, water-solublephthalocyanines can be obtained after known procedures (DE1569783,DE1569729, DE2021257, DE1794298). The synthesis and use of such metalphthalocyanines for the use as photoactivators are also known (DE0081462and references cited therein).

A suitable method to obtain water-soluble phthalocyanine is theintroduction of sulfonate groups.

The introduction can be done, for example, by sulfonation of theunsubstituted metal phthalocyanine.

Generally, the sulfonated phthalocyanines are not pure substances, butcomplex mixtures of different positional isomers. The SO₃H-group can belocated at position 3, 4, 5 or 6. Also the degree of sulfonation isvarying and normally not whole-numbered. For example, a tetra sodiumsalt of the Zinc phthalocyanine can be prepared after known procedure[J. Griffiths et al., Dyes and Pigments, Vol 33, 65-78 (1997) andliterature cited therein].

Another method to obtain a sulfonated metal phthalocyanine is reacting asulfophthalic acid with a metal salt, urea and a molybdate catalyst in amelt condensation. The obtained phthalocyanine is also a mixture ofisomers, but in this case only position isomers are found.

The position of the sulfonation is determined by the correspondingphthalic acid. If 4-sulfophthalic acid is used, a tetrasulfonated metalphthalocyanine with sulfonic acid groups exclusively in position 4 or 5is obtained.

The content of sulfonic acid groups can be adjusted by addition ofphthalic acid. Hence with this melt process sulfonated Zincphthalocyanine derivatives having a degree of sulfonation between DS=1-4can be prepared.

In the present application, a phthalocyanine molecule is being linkedthrough covalent bonds with a mono-azo dye molecule via specific linkinggroups. A convenient way to realize this linkage is the synthesis of ametal phthalocyanine sulfonyl chloride by a sulfochlorination reactionafter known procedures (DE2812261, DE0153278). By varying the amount ofthe sulfochlorination agent, the desired degree of sulfochloride contentcan be adjusted. The sulfochlorination reaction of phthalocyaninesgenerally leads to a main product, but as by-products small amounts oflower or higher degree of sulfonyl chloride groups are detected.

The resulting reactive phthalocyanine-sulfonylchloride can then bereacted further with a suitable dye having an amino group.

To illustrate the synthesis, the following synthetic examples leading tozinc and aluminium phthalocyanines linked with amino-functionalizedazo-dyes are given. The syntheses are performed as shown in thefollowing scheme. From the possible positional isomers, only one isshown. The formation of the side products (degree of SO₃R and SO₂Cl) isnot shown.

The synthesis of Zinc phthalocyanine derivatives with a lower degree ofsulfonation and analogous activation and coupling to the correspondingZinc phthalocyanine azo dyes is also possible.

The synthesis of exactly trisulfonated zinc phthalocyanine derivativesis known from literature [J. E. van Lier, Journ. Med. Chem. (1997), 40(24) 3897] as a product from ring expansion reaction of borontri(4-sulfo)subphthalocyanine.

The synthesis of less sulfonated metallated phthalocyanines can also beperformed by a modified sulfonation reaction, i.e. by shortening ofreaction time and/or reduction of reaction temperature.

A further aspect of the invention is a shading process for textile fibermaterials characterized by treating the textile fiber material with acomposition comprising at least one Zn—, Ca—, Mg—, Na—, K—, Al, Si—,Ti—, Ge—, Ga—, Zr—, In— or Sn— phthalocyanine compound of formula (1)

(PC)-L-(D) (1) to which at least one mono-azo dyestuff is attachedthrough a covalent bonding via a linking group L wherein

-   PC is the metal-containing phthalocyanine ring system;-   D is the radical of a mono-azo dyestuff; and-   L is a group

wherein

-   -   R₂₀ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy or halogen;    -   R₂₁ is independently D, hydrogen, OH, Cl or F, with the proviso        that at least one is D;    -   R₁₀₀ is C₁-C₈alkylene;    -   * is the point of attachment of PC;    -   # is the point of attachment for the dye.

In such a shading process the compounds of the instant invention aretypically used in a detergent formulation. The amount of the compoundsused is, for example, from 0.0001 to 1% by weight, preferably from 0.001to 0.5% by weight, based on the weight of the textile material.

As for the following, the term shading composition is meant to encompassalso the composition as such.

Also within the scope of the instant invention is a shading compositioncomprising at least one Zn—, Ca—, Mg—, Na—, K—, Al, Si—, Ti—, Ge—, Ga—,Zr—, In— or Sn— phthalocyanine compound of formula (1) (PC)-L-(D) (1) towhich at least one mono-azo dyestuff is attached through a covalentbonding via a linking group L wherein

-   PC is the metal-containing phthalocyanine ring system;-   D is the radical of a mono-azo dyestuff; and-   L is a group

wherein

-   -   R₂₀ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy or halogen;    -   R₂₁ is independently D, hydrogen, OH, Cl or F, with the proviso        that at least one is D;    -   R₁₀₀ is C₁-C₈alkylene;    -   * is the point of attachment of PC;    -   # is the point of attachment of the dye.

The composition and process comprising at least one compound of formula(1) produces a relative hue angle of 220-320° and the compounds offormula (1) are not light stable. That means that the compounds offormula (1) of the shading composition are destroyed by light. Visiblelight (400 to 800 nm) is meant by the term “light”. Preferably, it issunlight.

Color coordinates and color differences are expressed using theinternationally standardized CIELAB tristimulus values:

-   a*=red−green (+, −)-   b*=yellow−blue (+, −)-   L*=lightness (light=100)-   C*=chroma

H*=hue (angle of 0°=red, 90°=yellow, 180°=green, 270°=blue),

and the color differences ΔE*, ΔH*, ΔC*, ΔL*, Δa*, and Δb*, togetherwith an identification number of the sample.

This internationally accepted system has been developed by CIE(“Commission Internationale de I'Éclairage”). It is for example part ofDIN 6174: 1979-01 as well as DIN 5033-3: 1992-07.

The composition and process comprising at least one compound of formula(1) produces a relative hue angle of 220-320° and the compounds offormula (1) are degraded when the composition is exposed to sunlight.Preferably, the compounds of formula (1) are destroyed by light,preferably sunlight, when they are applied onto the textile fibermaterial.

The composition comprising at least one compound of formula (1) producesa relative hue angle of 220-320° and the decrease rate of the compoundsof formula (1) is at least 1% per 2 hours, preferably at least 2% whenthe composition is exposed to (sun)light.

For example, the degradation of the components can be determinedspectrophotometrically.

Preferably, the degradation of the compound of formula (1) when appliedonto the textile fiber material does not change the color of the textilefiber material, even if the textile fiber material is treated with thesecompounds repeatedly.

Examples of suitable textile fiber materials are materials made of silk,wool, polyamide, acrylics or polyurethanes, and, in particular,cellulosic fiber materials and blends of all types. Such fiber materialsare, for example, natural cellulose fibers, such as cotton, linen, juteand hemp, and regenerated cellulose. Preference is given to textilefiber materials made of cotton. Also suitable are hydroxyl-containingfibers which are present in mixed fabrics, for example mixtures ofcotton with polyester fibers or polyamide fibers.

The shading composition may be in any physical form, preferably in asolid or liquid form. Typical solid forms are powder, tablets orgranulates.

Granulates are preferred as solid formulation.

A further aspect of the invention is a shading composition as describedabove in form of a granule comprising

-   -   a) from 2 to 75% by weight (wt-%) of at least one phthalocyanine        compound of formula (1) as defined hereinbefore, based on the        total weight of the granulate,    -   b) from 10 to 95 wt-% of at least one further additive, based on        the total weight of the granulate, and    -   c) from 0 to 15 wt-% water, based on the total weight of the        granulate.

The sum of the wt-% of components a)-c) is always 100%.

Usually, the inventive shading process is part of a laundry washingprocess. It can be part of any step of the laundry washing process(pre-soaking, main washing and after-treatment). The process can becarried out in a washing machine as well as by hand. The usualtemperature is between 5° C. and 95° C.

The washing or cleaning agents are usually formulated that the washingliquor has a pH value of about 6.5-11, preferably 7.5-11 during thewhole washing procedure. The liquor ratio in the washing process isusually 1:4 to 1:40, preferably 1:4 to 1:30.

The washing procedure is usually done in a washing machine.

There are various types of washing machines, for example:

-   -   top-loader-washing machines with a verticle rotating axis; these        machines, which have usually a capacity of about 45 to 83        litres, are used for washing processes at temperatures of        10-50° C. and washing cycles of about 10-60 minutes. Such types        of washing machines are often used in the USA;    -   front-loader-washing machine with a horizontal rotating axis;        these machines, which have usually a capacity of about 8 to 15        litres, are used for washing processes at temperatures of        30-95° C. and washing cycles of about 10-60 minutes. Such types        of washing machines are often used in Europe;    -   top-loader-washing machines with a verticle rotating axis; these        machines, which have usually a capacity of about 26 to 52        litres, are used for washing processes at temperatures of        5-25° C. and washing cycles of about 8-15 minutes. Such types of        washing machines are often used in Japan.

The composition according to the invention can also be used in a soakingprocess, where the stained textiles are left for 0.1-24 hours in asolution or suspension of the detergent and/or bleaching laundryadditive without agitation. Soaking can take place for example in abucket or in a washing machine. Usually the textiles are washed and/orrinsed after the soaking process.

The granulates according to the invention can be encapsulated or not.

Encapsulating materials include especially water-soluble andwater-dispersible polymers and waxes. Of those materials, preference isgiven to polyethylene glycols, polyamides, polyacrylamides, polyvinylalcohols, polyvinylpyrrolidones, gelatin, hydrolyzed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate withmethacrylate and methacrylic acid, and poly-methacrylates.

The granulates according to the invention contain from 2 to 75 wt-%,preferably from 2 to 60 wt-%, especially from 5 to 55 wt-%, of componenta), based on the total weight of the granulate.

The granulates in the formulations according to the invention containfrom 10 to 95 wt-%, preferably from 10 to 85 wt-%, especially from 10 to80 wt-%, of at least one further additive (component b)), based on thetotal weight of the granulate.

Such further additives may be anionic or non-ionic dispersing agents;water-soluble organic polymers; inorganic salts; low-molecular-weightorganic acids or salts thereof or wetting agents in an amount of from10% to 80% by weight; disintegrants such as, for example, powdered orfibrous cellulose, microcrystalline cellulose; fillers such as, forexample, dextrin; water-insoluble or water-soluble dyes or pigments; andalso dissolution accelerators and optical brighteners. Aluminiumsilicates such as zeolites, and also compounds such as talc, kaolin,TiO₂, SiO₂ or magnesium trisilicate may also be used in small amounts,for example 0-10% by weight, based on the weight of the totalformulation.

The anionic dispersing agents used are, for example, the commerciallyavailable water-soluble anionic dispersing agents for dyes, pigmentsetc.

The following products, especially, come into consideration:condensation products of aromatic sulfonic acids and formaldehyde,condensation products of aromatic sulfonic acids with unsubstituted orchlorinated biphenyls or biphenyl oxides and optionally formaldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerizedorganic sulfonic acids, sodium salts of polymerizedalkylnaphthalenesulfonic acids, sodium salts of polymerizedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalene-methanesulfonates, ligno- or oxyligno-sulfonates orheterocyclic polysulfonic acids. Especially suitable anionic dispersingagents are condensation products of naphthalene-sulfonic acids withformaldehyde, sodium salts of polymerized organic sulfonic acids,(mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynucleararylsulfonates, sodium salts of polymerized alkylbenzenesulfonic acid,lignosulfonates, oxylignosulfonates and condensation products ofnaphthalenesulfonic acid with a polychloromethylbiphenyl.

Suitable non-ionic dispersants are especially compounds having a meltingpoint of, prefer-ably, at least 35° C. that are emulsifiable,dispersible or soluble, for example the following compounds:

-   1. fatty alcohols having from 8 to 22 carbon atoms, especially cetyl    alcohol;-   2. addition products of, preferably, from 2 to 80 mol of alkylene    oxide, especially ethylene oxide, wherein some of the ethylene oxide    units may have been replaced by substituted epoxides, such as    styrene oxide and/or propylene oxide, with higher unsaturated or    saturated monoalcohols, fatty acids, fatty amines or fatty amides    having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl    phenols, benzyl phenols or alkyl phenols, the alkyl radicals of    which have at least 4 carbon atoms;-   3. alkylene oxide, especially propylene oxide, condensation products    (block polymers);-   4. ethylene oxide/propylene oxide adducts with diamines, especially    ethylenediamine;-   5. reaction products of a fatty acid having from 8 to 22 carbon    atoms and a primary or secondary amine having at least one    hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or alkylene    oxide addition products of such hydroxyalkyl-group-containing    reaction products;-   6. sorbitan esters, preferably with long-chain ester groups, or    ethoxylated sorbitan esters, such as polyoxyethylene sorbitan    monolaurate having from 4 to 10 ethylene oxide units or    polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene    oxide units;-   7. addition products of propylene oxide with a tri- to hexa-hydric    aliphatic alcohol having from 3 to 6 carbon atoms, e.g. glycerol or    pentaerythritol; and-   8. fatty alcohol polyglycol mixed ethers, especially addition    products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol    of propylene oxide with aliphatic monoalcohols having from 8 to 22    carbon atoms.

Especially suitable non-ionic dispersants are surfactants of formula

R₂₂—O-(alkylene-O)_(n)—R₂₃  (10),

wherein

-   R₂₂ is C₈-C₂₂alkyl or C₈-C₁₈alkenyl,-   R₂₃ is hydrogen; C₁-C₄alkyl; a cycloaliphatic radical having at    least 6 carbon atoms or benzyl, C₈-C₁₂alkenyl-   “alkylene” is an alkylene radical having from 2 to 4 carbon atoms    and-   n is an integer from 1 to 60.

The substituents R₂₂ and R₂₃ in formula (10) are advantageously each thehydrocarbon radical of an unsaturated or, preferably, saturatedaliphatic monoalcohol having from 8 to 22 carbon atoms. The hydrocarbonradical may be straight-chain or branched. R₂₂ and R₂₃ are preferablyeach independently of the other an alkyl radical having from 9 to 14carbon atoms.

Aliphatic saturated monoalcohols that come into consideration includenatural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetyl alcoholor stearyl alcohol, and also synthetic alcohols, e.g. 2-ethylhexanol,2,4-dimethyl-pentan-2-ol, octan-2-ol, isononyl alcohol,trimethylhexanol, trimethylnonyl alcohol, decanol, C₉-C₁₁oxo-alcohol,tridecyl alcohol, isotridecyl alcohol and linear primary alcohols(Alfols) having from 8 to 22 carbon atoms. Some examples of such Alfolsare Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol(16-18). (“Alfol” is a registered trade mark of the Sasol Corp.).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol,hexadecenyl alcohol and oleyl alcohol.

The alcohol radicals may be present singly or in the form of mixtures oftwo or more components, e.g. mixtures of alkyl and/or alkenyl groupsthat are derived from soybean fatty acids, palm kernel fatty acids ortallow oils. Such granules are for example described in WO 2006/024612.

Instead of or in addition to the dispersing agent or agents, thegranulates according to the invention may comprise a water-solubleorganic polymer, which may also have dispersing properties. Suchpolymers may be used singly or as mixtures of two or more polymers. Aswater-soluble polymers (which may, but need not, have film-formingproperties), there come into consideration, for example, gelatins,polyacrylates, polymethacrylates, copolymers of ethyl acrylate, methylmethacrylate and methacrylic acid (ammonium salt),polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers ofvinylpyrrolidone with long-chain olefins,poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers ofvinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers ofvinyl-pyrrolidone/dimethylaminopropyl acrylamides, quaternisedcopolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates,terpolymers of vinylcaprolactam/vinyl-pyrrolidone/dimethylaminoethylmethacrylates, copolymers of vinylpyrrolidone andmethacrylamidopropyltrimethylammonium chloride, terpolymers ofcaprolactam/vinyl-pyrrolidone/dimethylaminoethyl methacrylates,copolymers of styrene and acrylic acid, polycarboxylic acids,polyacrylamides, carboxymethyl cellulose, hydroxymethyl cellulose,polyvinyl alcohols, hydrolyzed and non-hydrolyzed polyvinyl acetate,copolymers of maleic acid with unsaturated hydrocarbons and also mixedpolymerization products of the mentioned polymers. Further suitablesubstances are polyethylene glycol (MW=2000−20 000), copolymers ofethylene oxide with propylene oxide (MW>3500), condensation products(block polymerization products) of alkylene oxide, especially propyleneoxide, copolymers of vinylpyrrolidone with vinyl acetate, ethyleneoxide-propylene oxide addition products with diamines, especiallyethylenediamine, polystyrenesulfonic acid, polyethylene-sulfonic acid,copolymers of acrylic acid with sulfonated styrenes, gum arabic,hydroxypropyl methylcellulose, sodium carboxymethyl cellulose,hydroxypropyl methylcellulose phthalate, maltodextrin, starch, sucrose,lactose, enzymatically modified and subsequently hydrated sugars, as areobtainable under the name “Isomalt”, cane sugar, polyaspartic acid andtragacanth.

Among those water-soluble organic polymers, special preference is givento carboxymethyl cellulose, polyacrylamides, polyvinyl alcohols,polyvinylpyrrolidones, gelatins, hydrolyzed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, maltodextrins,polyaspartic acid and also polyacrylates and polymethacrylates.

For use as inorganic salts there come into consideration carbonates,hydrogen carbonates, phosphates, polyphosphates, sulfates, silicates,sulfites, borates, halides and pyro-phosphates, preferably in the formof alkali metal salts. Preference is given to water-soluble salts suchas, for example, alkali metal chlorides, alkali metal phosphates, alkalimetal carbonates, alkali metal polyphosphates and alkali metal sulfatesand water-soluble salts used in washing agent and/or washing agentadditive formulations.

The optical brighteners may be selected from a wide range of chemicaltypes such as 4,4′-bis-(triazinylamino)-stilbene-2,2′-disulfonic acids,4,4′-bis-(triazol-2-yl)stilbene-2,2′-disulfonic acids,4,4′-(diphenyl)-stilbenes, 4,4′-distyryl-biphenyls,4-phenyl-4′-benzoxazolyl-stilbenes, stilbenzyl-naphthotriazoles,4-styryl-stilbenes, bis-(benzoxazol-2-yl) derivatives,bis-(benzimidazol-2-yl) derivatives, coumarines, pyrazolines,naphthalimides, triazinyl-pyrenes, 2-styryl-benzoxazole- or-naphthoxazole derivatives, benzimidazole-benzofuran derivatives oroxanilide derivatives. These optical brighteners are known andcommercially available. They are described inter alia in WO 2006/024612.

Especially preferred are the non-ionic or the anionic opticalbrighteners.

The granulates in the formulations according to the invention preferablyhave an average particle size of <500 μm. Greater preference is given tothe particle size of the granulates being from 40 to 400 μm.

A preferred embodiment of the present invention relates to granulatescomprising

-   -   a) from 2 to 75 wt-% of at least one phthalocyanine compound of        formula (1) as defined hereinbefore, based on the total weight        of the granulate,    -   b) from 10 to 95 wt-% of at least one further additive selected        from the group consisting of anionic or non-ionic dispersing        agents; water-soluble organic polymers; inorganic salt;        low-molecular-weight organic acid or a salt thereof; wetting        agents; disintegrants such as, for example, powdered or fibrous        cellulose, microcrystalline cellulose; fillers such as, for        example, dextrin; water-insoluble or water-soluble dyes or        pigments; dissolution accelerators; optical brighteners;        aluminium silicates; talc, kaolin, TiO₂, SiO₂ and magnesium        trisilicate, and    -   c) from 0 to 15 wt-% water, based on the total weight of the        granulate.

A more preferred embodiment of the present invention relates togranulates comprising

-   -   a) from 2 to 75 wt-% of at least one phthalocyanine compound of        formula (1) as defined hereinbefore, based on the total weight        of the granulate,    -   b) from 10 to 95 wt-% of at least one further additive selected        from the group consisting of anionic or non-ionic dispersing        agents; water-soluble organic polymers; inorganic salt;        low-molecular-weight organic acid or a salt thereof; wetting        agents; disintegrants such as, for example, powdered or fibrous        cellulose, microcrystalline cellulose; fillers such as, for        example, dextrin; water-insoluble or water-soluble dyes or        pigments; dissolution accelerators; optical brighteners;        aluminium silicates; talc, kaolin, TiO₂, SiO₂ and magnesium        trisilicate, and    -   c) from 0 to 15 wt-% water, based on the total weight of the        granulate.

Another embodiment of the invention is a composition, especially ashading composition, as described above in liquid form comprising

-   -   (a) 0.01-95 wt-%, preferably 1-80 wt-%, more preferably 5-70        wt-% of a phthalocyanine compound of formula (1) as defined        hereinbefore, based on the total weight of the liquid        formulation,    -   (b) 5-99.99 wt-%, preferably 20-99 wt-%, more preferably 30-95        wt-%, based on the total weight of the liquid formulation, of at        least one solvent and    -   (c) 0-10 wt-%, preferably 0-5 wt-%, more preferably 0-2 wt-%,        based on the total weight of the liquid formulation, of at least        one further additive.

As solvents, polar solvents are preferred. Especially preferred areC₁-C₄-alcohols or water.

If appropriate, the liquid formulation according to the invention canfurther comprise optional additives; examples are preservatives ormixtures of preservatives, such as chloroacetamide, triazine derivates,benzoisothiazolines, 2-methyl-2H-isothiazol-3 on,2-octyl-2H-isothiazol-3 on, 2-brom-2-nitropropan-1,3-diol or aqueousformaldehyde solution; Mg/Al silicates or mixtures of Mg/Al silicates,such as bentonite, montmorillonite, zeolites or highly disperse silicicacids; odour improvers and perfuming agent or mixtures thereof; antifoamagents or mixtures thereof; builders or mixtures thereof; protectivecolloids or mixtures thereof; stabilizers or mixtures thereof;sequestering agents and antifreeze agents or mixtures thereof, such aspropylene glycol.

A more preferred embodiment of the present invention relates to a liquidformulation comprising

-   -   (a) 0.01-95 wt-%, preferably 1-80 wt-%, more preferably 5-70        wt-% of a phthalocyanine compound of formula (1) as defined        hereinbefore, based on the total weight of the liquid        formulation,    -   (b) 5-99.99 wt-%, preferably 20-99 wt-%, more preferably 30-95        wt-%, based on the total weight of the liquid formulation, of        C₁-C₄-alcohols or water, and    -   (c) 0-10 wt-%, preferably 0-5 wt-%, more preferably 0-2 wt-%,        based on the total weight of the liquid formulation, of at least        one additive selected from the group consisting of        preservatives; Mg/Al silicates; odour improvers; perfuming        agent; antifoam agents; builders; protective colloids;        stabilizers; sequestering agents and antifreeze agents.

The shading composition according to the invention is used especially ina washing or softener formulation. Such a washing or softenerformulation may be in solid, liquid, gel-like or paste-like form, forexample in the form of a liquid, non-aqueous washing agent compositioncontaining not more than 5 wt-%, preferably from 0 to 1 wt-%, water andbased on a suspension of a builder substance in a non-ionic surfactant,for example as described in GB-A-2 158 454.

The washing formulations may also be in the form of powders or(super-)compact powders, in the form of single- or multi-layer tablets(tabs), in the form of washing agent bars, washing agent blocks, washingagent sheets, washing agent pastes or washing agent gels, or in the formof powders, pastes, gels or liquids used in capsules or in pouches(sachets).

However, the washing agent compositions are preferably in the form ofnon-aqueous formulations, powders, tabs or granules.

The present invention accordingly relates also to washing agentformulations comprising

-   I) from 5 to 70 wt-% A) of at least one anionic surfactant and/or B)    at least one non-ionic surfactant, based on the total weight of the    washing agent formulation,-   II) from 0 to 60 wt-% C) of at least one builder substance, based on    the total weight of the washing agent formulation,-   III) from 0 to 30 wt-% D) of at least one peroxide and, optionally,    at least one activator and/or at least one catalyst, based on the    total weight of the washing agent formulation, and-   IV) from 0.001 to 5 wt-% E) of granulate as defined above, based on    the total weight of the washing agent formulation,-   V) from 0 to 60 wt-% F) of at least one further additive, based on    the total weight of the washing agent formulation, and-   VI) from 0 to 5 wt-% G)water, based on the total weight of the    washing agent formulation.

The sum of the wt-% of components I)-VI) in a formulation is always100%.

The anionic surfactant A) can be, for example, a sulfate, sulfonate orcarboxylate surfactant or a mixture thereof. Preferred sulfates arethose having from 12 to 22 carbon atoms in the alkyl radical, optionallyin combination with alkyl ethoxysulfates in which the alkyl radical hasfrom 10 to 20 carbon atoms.

Preferred sulfonates are e.g. alkylbenzenesulfonates having from 9 to 15carbon atoms in the alkyl radical. The cation in the case of anionicsurfactants is preferably an alkali metal cation, especially sodium.

The anionic surfactant component may be, e.g., an alkylbenzenesulfonate,an alkylsulfate, an alkylethersulfate, an olefinsulfonate, analkanesulfonate, a fatty acid salt, an alkyl or alkenyl ethercarboxylate or an α-sulfofatty acid salt or an ester thereof. Preferredare alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkylgroup, alkylsulfates having 8 to 18 carbon atoms, alkylethersulfateshaving 8 to 22 carbon atoms, and fatty acid salts being derived frompalm oil or tallow and having 8 to 22 carbon atoms. The average molarnumber of ethylene oxide added in the alkylethersulfate is preferably 1to 22, preferably 1 to 10. The salts are preferably derived from analkaline metal like sodium and potassium, especially sodium. Highlypreferred carboxylates are alkali metal sarcosinates of formulaR₁₀₉—CO(R₁₁₀)CH₂COOM₁ in which R₁₀₉ is alkyl or alkenyl having 8-20carbon atoms in the alkyl or alkenyl radical, R₁₁₀ is C₁-C₄ alkyl and M₁is an alkali metal, especially sodium.

The nonionic surfactant component B) may be, e.g., primary and secondaryalcohol ethoxylates, especially the C₈-C₂₀ aliphatic alcoholsethoxylated with an average of from 1 to 20 moles of ethylene oxide permole of alcohol, and more especially the C₁₀-C₁₅ primary and secondaryaliphatic alcohols ethoxylated with an average of from 1 to 10 moles ofethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactantsinclude alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides(glucamide).

The total amount of anionic surfactant and nonionic surfactant ispreferably 5-50 wt-%, preferably 5-40 wt-% and more preferably 5-30wt-%. As to these surfactants it is preferred that the lower limit is 10wt-%.

The non-ionic surfactant B) can be, for example, a condensation productof from 3 to 8 mol of ethylene oxide with 1 mol of a primary alcoholhaving from 9 to 15 carbon atoms.

As builder substance C) there come into consideration, for example,alkali metal phos-phates, especially tripolyphosphates, carbonates orhydrogen carbonates, especially their sodium salts, silicates,aluminosilicates, polycarboxylates, polycarboxylic acids, organicphosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures ofthose compounds.

Especially suitable silicates are sodium salts of crystalline layeredsilicates of the formula NaHSi_(t)O_(2t+1).pH₂O orNa₂Si_(t)O_(2t+1).pH₂O wherein t is a number from 1.9 to 4 and p is anumber from 0 to 20.

Among the aluminosilicates, preference is given to those commerciallyavailable under the names zeolith A, B, X and HS, and also to mixturescomprising two or more of those components. Zeolith A is preferred.

Among the polycarboxylates, preference is given topolyhydroxycarboxylates, especially citrates, and acrylates and alsocopolymers thereof with maleic anhydride. Preferred poly-carboxylicacids are nitrilotriacetic acid, ethylenediaminetetraacetic acid andethylene-diamine disuccinate either in racemic form or in theenantiomerically pure (S,S) form.

Phosphonates or aminoalkylenepoly(alkylenephosphonates) that areespecially suitable are alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonicacid), ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminN,N,N′,N′ tetrakis methanphosphonic acid anddiethylenetriaminepentamethylenephosphonic acid, as well as the saltstherefrom. Also preferred polyphosphonates have the following formula

wherein

-   R₁₁₁ is CH₂PO₃H₂ or a water soluble salt thereof and-   d is an integer of the value 0, 1, 2 or 3    are preferred.

Especially preferred are the polyphosphonates wherein b is an integer ofthe value of 1.

Suitable peroxide components D) include, for example, the organic andinorganic peroxides (like sodium percarbonate or sodium perborate) knownin the literature and available commercially that bleach textilematerials at conventional washing temperatures, for example at from 5 to95° C.

The amount of the peroxide or the peroxide-forming substance ispreferably 0.5-30% by weight, more preferably 1-20% by weight andespecially preferably 1-15% by weight.

It is, however, also possible that no peroxide or peroxide formingsubstance is present.

As the peroxide component D) there come into consideration everycompound which is capable of yielding hydrogen peroxide in aqueoussolutions, for example, the organic and inorganic peroxides known in theliterature and available commercially that bleach textile materials atconventional washing temperatures, for example at from 5 to 95° C.

The organic peroxides are, for example, mono- or poly-peroxides, ureaperoxides, a combination of a C₁-C₄alkanol oxidase and C₁-C₄alkanol(Such as methanol oxidase and ethanol as described in WO95/07972),alkylhydroxy peroxides, such as cumene hydroperoxide and t-butylhydroperoxide, organic mono peracids of formula

wherein

-   M signifies hydrogen or a cation,-   R₁₁₂ signifies unsubstituted C₁-C₁₈alkyl; substituted C₁-C₁₈alkyl;    unsubstituted aryl; substituted aryl; —(C₁-C₆alkylene)-aryl, wherein    the alkylene and/or the alkyl group may be substituted; and    phthalimidoC₁-C₈alkylene, wherein the phthalimido and/or the    alkylene group may be substituted. Preferred mono organic peroxy    acids and their salts are those of formula

wherein

-   M signifies hydrogen or an alkali metal, and-   R′₁₁₂ signifies unsubstituted C₁-C₄alkyl; phenyl;    —C₁-C₂alkylene-phenyl or phthalimidoC₁-C₈alkylene.

Especially preferred is CH₃COOOH and its alkali salts.

Especially preferred is also ε-phthalimido peroxy hexanoic acid and itsalkali salts.

Instead of the peroxy acid it is also possible to use organic peroxyacid precursors and H₂O₂. Such precursors are the correspondingcarboxyacid or the corresponding carboxyanhydrid or the correspondingcarbonylchlorid, or amides, or esters, which can form the peroxy acidson perhydrolysis. Such reactions are commonly known.

Peroxy acids may also be generated from precursers such as bleachactivators, that is to say compounds that, under perhydrolysisconditions, yield unsubstituted or substituted perbenzo- and/orperoxo-carboxylic acids having from 1 to 10 carbon atoms, especiallyfrom 2 to 4 carbon atoms. Suitable bleach activators include thecustomary bleach activators, mentioned at the beginning, that carry O-and/or N-acyl groups having the indicated number of carbon atoms and/orunsubstituted or substituted benzoyl groups. Preference is given topolyacylated alkylenediamines, especially tetraacetylethylenediamine(TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU),N,N-diacetyl-N,N-dimethylurea (DDU), acylated triazine derivatives,especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),compounds of formula:

wherein R₁₁₄ is a sulfonate group, a carboxylic acid group or acarboxylate group, and wherein R₁₁₃ is linear or branched (C₇-C₁₅)alkyl,especially activators known under the names SNOBS, SLOBS and DOBA,acylated polyhydric alcohols, especially triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran, and also acetylatedsorbitol and mannitol and acylated sugar derivatives, especiallypentaacetylglucose (PAG), sucrose polyacetate (SUPA),pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well asacetylated, optionally N-alkylated glucamine and gluconolactone. It isalso possible to use the combinations of conventional bleach activatorsknown from German Patent Application DE-A-44 43 177. Nitrile compoundsthat form peroxyimidic acids with peroxides also come into considerationas bleach activators.

Also suitable are diperoxyacids, for example, 1,12-diperoxydodecanedioicacid (DPDA), 1,9-diperoxyazelaic acid, diperoxybrassilic acid;diperoxysebasic acid, diperoxyisophthalic acid,2-decyldiperoxybutane-1,4-diotic acid and 4,4′-sulphonylbisperoxybenzoicacid.

Preferably, however, inorganic peroxides are used, for examplepersulfates, perborates, percarbonates and/or persilicates.

Example of suitable inorganic peroxides are sodium perboratetetrahydrate or sodium percarbonate monohydrate, inorganic peroxyacidcompounds, such as for example potassium monopersulphate (MPS). Iforganic or inorganic peroxyacids are used as the peroxygen compound, theamount thereof will normally be within the range of about 1-10 wt-%,preferably from 2-8 wt-%.

All these peroxy compounds may be utilized alone or in conjunction witha peroxyacid bleach precursor and/or an organic bleach catalyst notcontaining a transition metal. Generally, the bleaching composition ofthe invention can be suitably formulated to contain from 2 to 35 wt-%,preferably from 5 to 25 wt-%, of the peroxy bleaching agent.

Peroxyacid bleach precursors are known and amply described inliterature, such as in the British Patents 836988; 864,798; 907,356;1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522;EP-A-0174132; EP-A-0120591; and U.S. Pat. Nos. 1,246,339; 3,332,882;4,128,494; 4,412,934 and 4,675,393. Preferred are transition metalcatalysts disclosed in WO 01/05925), especially preferred the 1:1Mn(III) complexes.

Another useful class of peroxyacid bleach precursors is that of thecationic i.e. quaternary ammonium substituted peroxyacid precursors asdisclosed in U.S. Pat. Nos. 4,751,015 and 4,397,757, in EP-A0284292 andEP-A-331,229. Examples of peroxyacid bleach precursors of this classare: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonatechloride—(SPCC), N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammoniumchloride —(ODC), 3-(N,N,N-trimethyl ammonium) propylsodium-4-sulphophenyl carboxylate and N,N,N-trimethyl ammoniumtoluoyloxy benzene sulphonate.

A further special class of bleach precursors is formed by the cationicnitriles as disclosed in EP-A-303,520, WO 96/40661 and in EuropeanPatent Specification No.'s 458,396, 790244 and 464,880.

Any one of these peroxyacid bleach precursors can be used in the presentinvention, though some may be more preferred than others.

Of the above classes of bleach precursors, the preferred classes are theesters, including acyl phenol sulphonates and acyl alkyl phenolsulphonates; the acyl-amides; and the quaternary ammonium substitutedperoxyacid precursors including the cationic nitriles.

Examples of said preferred peroxyacid bleach precursors or activatorsare sodium-4-benzoyloxy benzene sulphonate (SBOBS); N,N,N′N′-tetraacetylethylene diamine (TAED); sodium-1-methyl-2-benzoyloxybenzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; SPCC;trimethyl ammonium toluoyloxy-benzene sulphonate; sodiumnonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethylhexanoyl-oxybenzene sulphonate (STHOBS); and the substituted cationicnitriles.

The precursors may be used in an amount of up to 12%, preferably from1-10% by weight, of the composition.

It will be understood that mixtures of inorganic and/or organicperoxides can also be used. The peroxides may be in a variety ofcrystalline forms and have different water contents, and they may alsobe used together with other inorganic or organic compounds in order toimprove their storage stability.

The peroxides are added to the agent preferably by mixing thecomponents, for example using a screw metering system and/or a fluidisedbed mixer.

The agents may comprise, in addition to the combination according to theinvention, one or more optical brighteners, for example from the classbis-triazinylamino-stilbenedisulfonic acid,bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl orbis-benzofuranylbiphenyl, a bis-benzoxalyl derivative,bis-benzimidazolyl derivative or coumarin derivative or a pyrazolinederivative.

The detergents used will usually contain one or more auxiliaries such assoil suspending agents, for example sodium carboxymethylcellulose; saltsfor adjusting the pH, for example alkali or alkaline earth metalsilicates; foam regulators, for example soap; salts for adjusting thespray drying and granulating properties, for example sodium sulphate;perfumes; and also, if appropriate, antistatic and softening agents;such as smectite clays; photobleaching agents; pigments; and/or shadingagents. These constituents preferably should, of course, be stable toany bleaching system employed. Such auxiliaries can be present in anamount of, for example, 0.1 to 20 wt-%, preferably 0.5 to 10 wt-%,especially 0.5 to 5 wt-%, based on the total weight of the detergent.

Furthermore, the detergent can optionally contain enzymes. Enzymes canbe added to detergents for stain removal. The enzymes usually improvethe performance on stains that are either protein- or starch-based, suchas those caused by blood, milk, grass or fruit juices. Preferred enzymesare cellulases, proteases, amylases and lipases. Preferred enzymes arecellulases and proteases, especially proteases. Cellulases are enzymeswhich act on cellulose and its derivatives and hydrolyze them intoglucose, cellobiose, cellooligosaccharide. Cellulases remove dirt andhave the effect of mitigating the roughness to the touch. Examples ofenzymes to be used include, but are by no means limited to, thefollowing:

proteases as given in U.S. Pat. No. B-6,242,405, column 14, lines 21 to32;lipases as given in U.S. Pat. No. B-6,242,405, column 14, lines 33 to 46and as given in WO 0060063;amylases as given in U.S. Pat. No. B-6,242,405, column 14, lines 47 to56; andcellulases as given in U.S. Pat. No. B-6,242,405, column 14, lines 57 to64.

Commercially available detergent proteases, such as Alcalase®,Esperase®, Everlase®, Savinase®, Kannase® and Durazym®, are sold e.g. byNOVOZYMES A/S.

Commercially available detergent amylases, such as Termamyl®, Duramyl®,Stainzyme®, Natelase®, Ban® and Fungamyl®, are sold e.g. by NOVOZYMESA/S.

Commercially available detergent ellulases, such as Celluzyme®,Carezyme® and Endolase®, are sold e.g. by NOVOZYMES A/S.

Commercially available detergent lipases, such as Lipolase®, LipolaseUltra® and Lipoprime®, are sold e.g. by NOVOZYMES A/S.

Suitable mannanases, such as Mannanaway®, are sold by NOVOZYMES A/S.

The enzymes can optionally be present in the detergent. When used, theenzymes are usually present in an amount of 0.01-5 wt-%, preferably0.05-5 wt-% and more preferably 0.1-4 wt-%, based on the total weight ofthe detergent.

Further preferred additives to the agents according to the invention aredye fixing agents and/or polymers which, during the washing of textiles,prevent staining caused by dyes in the washing liquor that have beenreleased from the textiles under the washing conditions. Such polymersare preferably polyvinylpyrrolidones, polyvinylimidazole orpolyvinylpyridine-N-oxides which may have been modified by theincorporation of anionic or cationic substituents, especially thosehaving a molecular weight in the range of from 5000 to 60000, moreespecially from 5000 to 50000. Such polymers are usually used in anamount of from 0.01 to 5 wt-%, preferably 0.05 to 5 wt-%, especially 0.1to 2 wt-%, based on the total weight of the detergent. Preferredpolymers are those given in WO-A-02/02865 (see especially page 1, lastparagraph and page 2, first paragraph).

The granulates are prepared according to known methods. Any known methodis suitable to produce granules comprising the inventive mixture.Continuous or discontinuous methods are suitable, Continuous methods,such as spray drying or fluidised bed granulation processes arepreferred.

Especially suitable are spray-drying processes in which the activeingredient solution is sprayed into a chamber with circulating hot air.The atomisation of the solution is carried out using single or binarynozzles or is brought about by the spinning effect of a rapidly rotatingdisc. In order to increase the particle size, the spray-drying processmay be combined with additional agglomeration of the liquid particleswith solid nuclei in a fluidised bed that forms an integral part of thechamber (so-called fluidised spray). The fine particles (<100 μm)obtained by a conventional spray-drying process may, if necessary afterbeing separated from the exhaust gas flow, be fed as nuclei, withoutbeing further treated, directly into the spray cone of the atomiser ofthe spray-dryer, for the purpose of agglomeration with the liquiddroplets of the active ingredient. During the granulation step, thewater can be rapidly removed from the solutions comprisingphthalocyanine compound, and, where appropriate, further additives, andit is expressly intended that agglomeration of the droplets forming inthe spray cone, i.e. the agglomeration of droplets with solid particles,will take place. Preference is given to the use of agglomerationprocesses to produce the granulates according to the invention becausesuch processes usually yield a higher bulk weight so that the granulateshave better compatibility with washing agent formulations.

The amount of (PC)-L-Dye compounds described herein before in thegranulate, is for example, from to 0.01 to 20 wt-%, preferably from 0.01to 0.5 wt-% and very especially from 0.05 to 0.3 wt-%.

The washing agent formulation according to the invention can be preparedin a generally known manner.

A formulation in powder form can be prepared, for example, by firstpreparing an initial powder by spray-drying an aqueous slurry comprisingall of the afore-mentioned components except for components D) and E)and then adding the dry components D) and E) and mixing all of themtogether. It is also possible to start from an aqueous slurry which,although comprising components A) and C), does not comprise component B)or comprises only a portion of component B). The slurry is spray-dried;component E) is then mixed with component B) and added; and thencomponent D) is mixed in dry. The components are preferably mixed withone another in such amounts that a solid compact washing agentcomposition in granule form is obtained, having a specific weight of atleast 500 g/l.

In another preferred embodiment, the production of the washing agentcomposition is carried out in three steps. In the first step a mixtureof anionic surfactant (and, where appropriate, a small amount ofnon-ionic surfactant) and builder substance is prepared. In the secondstep that mixture is sprayed with the major portion of the non-ionicsurfactant and then, in the third step, peroxide and, where appropriate,catalyst, and the granulate according to the invention are added. Thatmethod is usually carried out in a fluidised bed. In a further preferredembodiment, the individual steps are not carried out completelyseparately, so that there is a certain amount of overlap between them.Such a method is usually carried out in an extruder, in order to obtaingranulates in the form of “megapearls”.

As an alternative thereto, the granulates according to the inventioncan, for the purpose of admixture with a washing agent in a post-dosingstep, be mixed with other washing agent components such as phosphates,zeolites, brighteners or enzymes.

A mixture of that kind for post-dosing of the granulates isdistinguished by a homogeneous distribution of the granulates accordingto the invention in the mixture and can consist of, for example, from 5to 50% granulates and from 95 to 50% sodium tripolyphosphate. Where thedark appearance of the granulate in the washing agent composition is tobe suppressed, this can be achieved, for example, by embedding thegranules in droplets of a whitish meltable substance (“water-solublewax”) or, preferably, by encapsulating the granules in a melt consistingof, for example, a water-soluble wax, as described in EP-B-0 323 407 B1,a white solid (e.g. titanium dioxide) being added to the melt in orderto reinforce the masking effect of the capsule.

The detergent may also be formulated as an aqueous liquid comprising5-50, preferably 10-35 wt-% of water or as a non-aqueous liquiddetergent, containing not more than 5, preferably 0-1 wt-% of water.Non-aqueous liquid detergent compositions can contain other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5wt-% to 90 wt-%, typically 10 wt-% to 50 wt-% of such carriers. Thedetergents can also be present as the so-called “unit liquid dose” form.

A further embodiment of the present invention is a fabric softenerformulation comprising

-   (a) a shading composition as described above, and-   (b) at least one fabric softener.

Fabric softeners, especially hydrocarbon fabric softeners, suitable foruse herein are selected from the following classes of compounds:

-   (i) Cationic quaternary ammonium salts. The counter ion of such    cationic quaternary ammonium salts may be a halide, such as chloride    or bromide, methyl sulphate, or other ions well known in the    literature. Preferably the counter ion is methyl sulfate or any    alkyl sulfate or any halide, methyl sulfate being most preferred for    the dryer-added articles of the invention.

Examples of cationic quaternary ammonium salts include but are notlimited to:

(1) Acyclic quaternary ammonium salts having at least two C₈ to C_(m)preferably O₁₂ to O₂₂ alkyl or alkenyl chains, such as:ditallowedimethyl ammonium methylsulfate, di(hydrogenatedtallow)dimethyl ammonium methylsulfate, di(hydrogenated tallow)dimethylammonium methylchloride, distearyldimethyl ammonium methyl-sulfate,dicocodimethyl ammonium methylsulfate and the like. It is especiallypreferred if the fabric softening compound is a water insolublequaternary ammonium material which comprises a compound having two C₁₂to C₁₈ alkyl or alkenyl groups connected to the molecule via at leastone ester link. It is more preferred if the quaternary ammonium materialhas two ester links present. An especially preferred ester-linkedquaternary ammonium material for use in the invention can be representedby the formula:

wherein each R₁₃₆ group is independently selected from C₁ to C₄ alkyl,hydroxyalkyl or C₂ to C₄ alkenyl groups; T is either —O—C(O)— or—C(O)—O—, and wherein each R₁₃₇ group is independently selected from C₈to C₂₈ alkyl or alkenyl groups; and e is an integer from 0 to 5.

A second preferred type of quaternary ammonium material can berepresented by the formula:

wherein R₁₃₆, e and R₁₃₇ are as defined above.

(2) Cyclic quaternary ammonium salts of the imidazolinium type such asdi(hydrogenated tallow)dimethyl imidazolinium methylsulfate,1-ethylene-bis(2-tallow-1-methyl) imidazolinium methylsulfate and thelike;

(3) Diamido quaternary ammonium salts such as: methyl-bis(hydrogenatedtallow amidoethyl)-2-hydroxethyl ammonium methyl sulfate, methylbi(tallowamidoethyl)-2-hydroxypropyl ammonium methylsulfate and thelike;

(4) Biodegradable quaternary ammonium salts such asN,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium methyl sulfate andN,N-di(tallowoyl-oxy-propyl)-N,N-dimethyl ammonium methyl sulfate.Biodegradable quaternary ammonium salts are described, for example, inU.S. Pat. Nos. 4,137,180, 4,767,547 and 4,789,491 incorporated byreference herein.

Preferred biodegradable quaternary ammonium salts include thebiodegradable cationic diester compounds as described in U.S. Pat. No.4,137,180, herein incorporated by reference.

(ii) Tertiary fatty amines having at least one and preferably two C₈ toC₃₀ preferably C₁₂ to C₂₂ alkyl chains. Examples include hardenedtallow-di-methylamine and cyclic amines such as 1-(hydrogenatedtallow)amidoethyl-2-(hydrogenated tallow) imidazoline. Cyclic amines,which may be employed for the compositions herein, are described in U.S.Pat. No. 4,806,255 incorporated by reference herein.

(iii) Carboxylic acids having 8 to 30 carbons atoms and one carboxylicgroup per molecule. The alkyl portion has 8 to 30, preferably 12 to 22carbon atoms. The alkyl portion may be linear or branched, saturated orunsaturated, with linear saturated alkyl preferred. Stearic acid is apreferred fatty acid for use in the composition herein. Examples ofthese carboxylic acids are commercial grades of stearic acid andpalmitic acid, and mixtures thereof, which may contain small amounts ofother acids.

(iv) Esters of polyhydric alcohols such as sorbitan esters or glycerolstearate. Sorbitan esters are the condensation products of sorbitol oriso-sorbitol with fatty acids such as stearic acid. Preferred sorbitanesters are monoalkyl. A common example of sorbitan ester is SPAN° 60(ICI) which is a mixture of sorbitan and isosorbide stearates.

(v) Fatty alcohols, ethoxylated fatty alcohols, alkylphenols,ethoxylated alkylphenols, ethoxylated fatty amines, ethoxylatedmonoglycerides and ethoxylated diglycerides.

(vi) Mineral oils, and polyols such as polyethylene glycol.

These softeners are more definitively described in U.S. Pat. No.4,134,838 the disclosure of which is incorporated herein by reference.Preferred fabric softeners for use herein are acyclic quaternaryammonium salts. Mixtures of the above mentioned fabric softeners mayalso be used.

The fabric softener formulation according to this invention comprisesabout 0.001-5 wt-%, preferably 0.001-3 wt-%, of the shading composition,based on the total weight of the fabric softener formulation.

The fabric softener formulation employed in the present inventionpreferably contains about 0.1 to about 95 wt-%, based on the totalweight of the fabric softening composition, of the fabric softenerformulation. Preferred is an amount of 0.5 to 50 wt-%, especially anamount of 2 to 50 wt-% and most preferably an amount of 2 to 30 wt-%.

The fabric softening composition may also comprise additives which arecustomary for standard commercial fabric softening compositions, forexample alcohols, such as ethanol, n-propanol, i-propanol, polyhydricalcohols, for example glycerol and propylene glycol; amphoteric andnonionic surfactants, for example carboxyl derivatives of imidazole,oxyethylated fatty alcohols, hydrogenated and ethoxylated castor oil,alkyl polyglycosides, for example decyl polyglucose anddodecylpolyglucose, fatty alcohols, fatty acid esters, fatty acids,ethoxylated fatty acid glycerides or fatty acid partial glycerides; alsoinorganic or organic salts, for example water-soluble potassium, sodiumor magnesium salts, non-aqueous solvents, pH buffers, perfumes, dyes,hydrotropic agents, antifoams, anti redeposition agents, enzymes,optical brighteners, antishrink agents, stain removers, germicides,fungicides, dye fixing agents or dye transfer inhibitors (as describedin WO-A-02/02865), antioxidants, corrosion inhibitors, wrinkle recoveryor wet soiling reduction agent, such as polyorganosiloxanes. The lattertwo additives are described in WO0125385.

Such additives are preferably used in an amount of 0 to 30 wt-%, basedon the total weight of the fabric softening composition. Preferred is anamount of 0 to 20 wt-%, especially an amount of 0 to 10 wt-% and mostpreferably an amount of 0 to 5 wt-%, based on the total weight of thefabric softening composition.

The fabric softener compositions are preferably in liquid aqueous form.The fabric softener compositions preferably contain a water content of25 to 90 wt-%, based on the total weight of the composition. Morepreferably the water content is 50 to 90 wt-%, especially 60 to 90 wt-%.

The fabric softener compositions preferably have a pH value from 2.0 to9.0, especially 2.0 to 5.0.

The fabric softener compositions can, for example, be prepared asfollows:

Firstly, an aqueous formulation of the cationic polymer is prepared asdescribed above. The fabric softener composition according to theinvention is usually, but not exclusively, prepared by firstly stirringthe active substance, i.e. the hydrocarbon based fabric softeningcomponent, in the molten state into water, then, where required, addingfurther desired additives and, finally, adding the formulation of thecationic polymer. The fabric softener composition can, for example, alsobe prepared by mixing a preformulated fabric softener with the cationicpolymer.

These fabric softener compositions are traditionally prepared asdispersions containing for example up to 30 wt-% of active material inwater. They usually have a turbid appearance. However, alternativeformulations usually containing actives at levels of 5 to 40 wt-% alongwith solvents can be prepared as microemulsions, which have a clearappearance (as to the solvents and the formulations see for example U.S.Pat. No. 5,543,067 and WO-A-98/17757).

Another aspect of the invention is the use of a compound as describedabove for the shading of textile materials.

Yet further aspects of the invention are a compound of formula (A)

a compound of formula (A1)

a compound of formula (B1)

a compound of formula (B2)

or a compound of formula (B4)

wherein M is H or Na. Thus, the compounds may be in the form of the freeacids or their corresponding sodium salts. When dissolved in water, thedegree of dissociation of the free acids depends on the pH value of thesolution.

All definitions and preferences described above apply equally for allaspects of the invention.

The following examples illustrate the invention.

General Procedures

The Zinc phthalocyanine sulfonic acid mixture with at least onesulfonylchloride group is prepared starting from unsubstituted Zincphthalocyanine. The first possibility is to sulfonate unsubstituted Zincphthalocyanine. The degree of sulfonation can be adjusted by thesulfonation time and the appropriate sulfonation temperature. Normally,the corresponding Zinc phthalocyanine sulfonic acid sodium salt isisolated. The Zinc phthalocyanine sulfonic acid derivative is activatedto a Zinc phthalocyanine sulfonylchloride derivative.

The synthesis of a Zinc phthalocyanine sulfonic acid mixture is alsopossible by direct activation of dried solid Zinc phthalocyaninesulfonic acid mixtures prepared according to literature procedures.

1a) Synthesis of a Zinc phthalocyanine sulfonic acid mixture with atleast one active sulfonyl chloride starting from Zinc phthalocyanine

A mixture of 16.55 ml (31.4 g) fuming sulfuric acid (20% free SO₃) and12.8 ml (24.8 g) fuming sulfuric acid (65% free SO₃) is stirred at 20°C. Into this solution, 12.5 g (0.0195 mol) Zinc phthalocyanine (90%active) is added within 5-10 minutes. The reaction mixture is heated to75° C. and kept for 30 minutes at that temperature. Then the reactionmixture is poured within 10 minutes into 330 g of a mixture of ice andwater. With sodium hydroxide (32% G/G) pH 7 is adjusted while thetemperature of the solution is kept below 25° C. The crude Zincphthalocyanine sulfonic acid is desalted by dialysis and freeze-dried.Yield: 13 g. 1.5 g of this dry mixture is suspended in 14.94 g (0.128mol) chlorosulfuric acid. The reaction mixture is heated to 87° C. andkept for 30 minutes. Within 45 minutes, 1.05 ml (1.72 g, 0.014 mol)thionyl chloride is added dropwise. The reaction mixture is kept at 87°C. for two more hours. Then the solution is allowed to cool down to 30°C. and poured within 10 minutes into 25 g of an ice/water mixture. Thetemperature of the solution is kept between 0-5° C. by further additionof ice. The formed precipitate is filtered off and washed with sodiumchloride solution (3%)

A mixture of bis- and tris-sulfonated Zinc phthalocyanine isomers isobtained (DS=2-3). Hence, the raw material is mainly a mixture ofdifferent Zinc phthalocyanine bis-sulfonicacid-mono-sulfonylchloride/Zinc phthalocyanine monosulfonicacid-monosulfonylchloride (1 active SO₂Cl group) and Zinc phthalocyaninemonosulfonic acid bis-sulfonylchloride/Zinc phthalocyaninebis-sulfonylchloride (2 active SO₂Cl) derivatives. The sulfonation ofthe Zinc phthalocyanine can also be performed with chlorosulfuric acid.

1b) Synthesis of a Zinc Phthalocyanine Sulfonic Acid Mixture with atLeast One Active Sulfonyl Chloride

The Zinc phthalocyanine tetrasulfonic acid sodium salt is a mixture ofdifferent isomers with an average degree of sulfonation about 3.6-3.8.It can be obtained by a sulfonation procedure of the unsubstituted Zincphthalocyanine according to known procedures. The main components arevarious isomers of tetrasulfonated and trisulfonated Zincphthalocyanines. Before the reaction the material must be dried bylyophilization or spray drying. The dried Zinc phthalocyaninetetrasulfonic acid sodium salt (3.6 mmol) is slowly added under stirringto chlorosulfuric acid (117.4 mmol) at room temperature. The reactionmixture is heated to 85-90° C. for 30 minutes and stirred for 1.5 hours.During 90 minutes at this temperature thionyl chloride (28.6 mmol) isadded dropwise. Stirring is continued for another 2 hours at 87° C. Thereaction mixture is cooled down to room temperature and added to anexcess of ice. The formed green precipitate is filtered off and washedwith aqueous sodium chloride (3%). The green intermediate is directlyused for the next reaction step. The raw material is mainly a mixture ofZinc phthalocyanine tris(sulfonic acid) monosulfonylchloride/Zincphthalocyanine bis(sulfonic acid)monosulfonylchloride (1 active SO₂Clgroup) and Zinc phthalocyanine bis(sulfonic acid)bis-sulfonyl-chloride/Zinc phthalocyanine monosulfonic acidbis-sulfonylchloride (2 active SO₂Cl) derivatives.

2) Synthesis of a Zinc Phthalocyanine Dye Conjugate

The crude moist Zinc phthalocyanine sulfonylchloride prepared from0.0195 mol Zinc phthalocyanine in 1a) is dissolved in ice-cold water andan aqueous solution (0.0195 mol) of the corresponding dye is addedwithin 5 minutes. The reaction mixture is adjusted to pH 7 with sodiumhydroxide (32%). The reaction mixture is heated to 50° C. and stirredfor 2 hours, afterwards cooled down to 25° C. and stirred another eighthours. During the reaction time, the reaction mixture is automaticallymaintained at pH 7 with sodium hydroxide (32%). The reaction ismonitored by TLC (solvent pyridine 25 ml/N,N-diethylamine 33ml/3-methylbutanol 17 ml/aqueous ammonia (25%) 25 ml) or by LC (solvent1 water/borax buffer pH=10, TBAHS, solvent 2 methanol/TBHAS with aZorbax column Eclipse XDB-Phenyl. The reaction mixture is worked-up whenthe coupling reaction is complete and no more free unbound dye isdetected.

Work-up and purification:

The reaction mixture is desalted by dialysis (cellulose tubes, MWCO12.000-14.000, 45 mm*vol/cm: 6.42, wall thickness: 20 μm) or bynanofiltration through a suitable membrane. The desalted reactionsolution contains the isomeric mixtures of covalently linked sulfonatedZinc phthalocyanine dye conjugates and tetrasulfonated Zincphthalocyanine as by-product. The obtained blue solution can be directlyused for the synthesis of liquid or solid formulations.

A solid Zinc phthalocyanine dye conjugate can be obtained bylyophilization of the desalted solution.

Because there are numerous possible isomers with regard to the positionof the sulfonic acid group and the sulfonamide linkage, only generalstructures are given. The sulfonic acid function can exist in the freeacid form or as in the sodium salt form or as a mixture thereof.

EXAMPLE A1 Synthesis of a Zinc Phthalocyanine Monoazo Dye Conjugate a)Synthesis of a Zinc Phthalocyanine Sulfonyl Chloride Derivative

2.0 g Zinc phthalocyanine tetrasulfonic acid sodium salt, 15 mlchlorosulfuric acid and 2.6 ml of thionyl chloride are reacted as givenin the general procedure 1b). The reaction mixture is given onto 50 gice. The precipitate is isolated as described above and directly usedfor further reactions.

b) Preparation of the Monoazo Dye:

I) Preparation of the coupling component: 0.05 mol ofN-(4-aminobenzoyl)-H-acid are suspended in 100 ml water and adjusted topH 7.5 with aqueous solution of 30% sodium hydroxide.

II) Suspension and diazotization of 1-aminonaphthalene: 7.14 g (0.05mol) 1-aminonaphthalene is suspended in a mixture of 100 ml water and 5ml hydrochloric acid (32%). The temperature of this suspension isincreased to 30° C. until a solution is formed. Again 12 ml ofhydrochloric acid (32%) is added. Afterwards the solution is cooled downto 0° C. with 120 g of ice. 11 ml of 4N sodium nitrite solution is addedslowly over the course of 15 minutes. During the addition, thetemperature of the solution must be kept below 4° C. Sulfamic acid (1M)is added to the solution to destroy the excess sodium nitrite. 0.05 molreaction solution are obtained.

III) Coupling: A solution of 0.05 mol of the coupling component preparedin I) is cooled down to 0° C. To that solution the 0.05 mol diazosuspension prepared in II) is added over the course of 30 minutes.Simultaneously, a pH of 7.5 and a temperature between 0-5° C. isadjusted with an aqueous (20%) solution of sodium carbonate. A violetsuspension is obtained. Reaction monitoring is done by LC. When thereaction is complete, the raw dye solution is desalted in a dialysistube at pH 8.5 and lyophilized.

Yield: 48.2 g, UV_(vis) λ_(max) 548 nm.

c) Synthesis of the Zinc Phthalocyanine Dye Conjugate

815 mg Zinc phthalocyanine monosulfonyl chloride from example Ala) aresuspended in 40 ml water at 0° C. A solution of 527 mg dye in 30 mldistilled water is added dropwise. The reaction mixture is reacted,worked-up, desalted and dried according to general procedure 2).

The product is obtained as a dark blue solid.

The characterization was done by UV_(vis)-spectroscopy (λ 540 andλ_(max) 672 nm) and MS.

The assignments of the detected structures are given in the followingtable.

Molecular weight (g/mol) structure 896

1470

816

1390

EXAMPLE A2 Synthesis of a Zinc Phthalocyanine Monoazo Triazine DyeConjugate

a) Preparation of the monoazo triazine dye

I) Synthesis of the monoazo intermediate. The monoazo1-naphthylamine-diazo to H-acid is prepared by diazotization ofcommercially available 1-aminonaphthalene, coupling to acetylated H-acidand finally, alkaline hydrolysis.

Acetylation of H-acid: 191.9 g (0.5 mol) H-acid (83%) is suspended in500 ml water and dissolved at pH 7 by the addition of 48.6 ml aqueousNaOH (30%). 92.1 g acetic acid anhydride is slowly added over the courseof 10 minutes. The reaction solution is cooled to 10° C. by the additionof 250 g ice; with 118.3 ml aqueous NaOH (30%) a pH of 7 is adjusted.Further 56.2 ml aqueous NaOH (30%) is added. A pH value of 10.5 ismaintained for 1 hour at a temperature of 30° C. by the addition of 4.8ml NaOH (30%). By addition of 32.9 ml aqueous HCl (32%), the solution isadjusted to a pH value of 7.2. The solution is cooled to 20° C. with 180g ice. The reaction solution has a weight of 1594 g containing 0.5 molof acetylated H-acid.

Suspension and diazotation of 1-naphthylamine: In a mixture of 800 mlwater and 40.0 ml aqueous HCl (32%) is added—under stirring—57.3 g (0.4mol) 1-naphthylamine as a melt. 97.2 ml HCl (32%) are added and thereaction solution is cooled to 0° C. with 530 g ice. Over the course of15 minutes, 90 ml of sodium nitrite solution (4N) is added. During theaddition, the temperature must not exceed 4° C. After further additionof 11 ml of sodium nitrite solution, the reaction mixture is stirred for30 minutes. 1 mol of sulfamic acid is added to destroy an excess ofnitrite.

Coupling: 1275 g (0.4 mol) of the acetylated H-acid (pH 4.8) is pouredover the course of 1 minute into the prepared diazo-suspension. A pHvalue of 7.5 is adjusted with 327 ml of sodium carbonate solution (20%G/V). The solution is stirred at room temperature for 12 hours. Totalvolume of reaction solution is around 3.4 liters.

Saponification: 340 ml NaOH (30%) is given to this reaction mixture. Thereaction mixture is heated to 90° C. and kept at this temperature for 3hours. By the addition of 292.5 ml HCl (32%) a pH value of 7.5 isadjusted. The violet suspension is stirred at room temperature for 12hours. The volume of the reactions solution is around 4 liters. Theformed precipitate is filtered off. 518.7 g of paste is obtained. Yield:84.4% (determined by titration with sodium nitrite).

II) first condensation: A suspension consisting of 14.23 g cyanuricchloride, 40 ml of water, 20 g of ice and 0.4 g of disodium hydrogentetraoxophosphate is prepared. Under stirring another 60 grams of iceare added. The reaction suspension is adjusted to pH=3.5 withhydrochloric acid. 1080.8 g of an aqueous solution containing 0.0735 molmonoazo intermediate is added over the course of 15 minutes to thereaction suspension. The reaction temperature during the addition iskept between 0-5° C. by addition of ice. Simultaneously pH 3.5 isadjusted with an aqueous solution (30%) of sodium hydroxide. Thereaction mixture is stirred for another hour at 0-5° C. at pH=4.Afterwards, the reaction mixture is allowed to reach room temperature.The resulting reaction mixture has a weight of 1677.7 g containing0.0735 mol.

III) second condensation: A solution of 4.02 g (0.0222 mol)m-phenylenediamine dihydrochloride in 25 ml water is poured over thecourse of one minute to 0.022 mol of the first condensation intermediateprepared according to II). By portionwise addition of 30% aqueous sodiumhydroxide solution, a pH value of 5 is maintained. The reaction isstirred at room temperature for 12 hours. The solution is desalted in adialysis tube and lyophilized.

b) Synthesis of the Zinc phthalocyanine dye conjugate: 800 mg Zincphthalocyanine monosulfonyl chloride from example 1a) is suspended into15 ml of water at 0° C. and tretated, reacted and worked-up as describedin the general procedure 2. The product is obtained as a dark-bluesolid.

The characterization was done by UV_(vis)-spectroscopy (λ 540 nm andλ_(max) 670 nm) and MS. The assignments of the detected structures aregiven in the following table.

Molecular weight (g/mol) structure 896

1570

816

2244

1490

In the above structural formulas the sulfonation of the PC ringsindicates the isomeric structures, which are obtained. The aboverepresentation includes, therefore, all possible structural isomers.

EXAMPLE A3 Synthesis of a Zinc Phthalocyanine Bis(Monoazo) Triazine DyeConjugate

a) Preparation of the bis(monoazo)-triazine dye

This dye can be prepared following two different synthetic procedures:

1) The Monoazo, 1-Naphthylamine-diazo to H-acid, is synthesizedaccording to the procedure given in example A2. Afterwards 2mole-equivalents of the monoazo are condensed to 1 mole-equivalent ofcyanuric chloride, the last condensation is done with 1 mole-equivalentof m-phenylenediamine.

I) An aqueous solution of 0.060 mol5-amino-4-hydroxy-3(naphthalen-1-ylazo)-naphthalene-2,7-disulfonic acidwas stirred at room temperature. A suspension consisting of 100 ml ofice water, 0.1 g disodium hydrogen tetraoxophosphate and 5.53 g (0.03mol) cyanuric chloride is added to the intermediate. The reactionmixture is adjusted and kept with aqueous sodium hydroxide solution(30%) at pH 7. After 30 minutes the reaction mixture is heated to 70° C.and pH 7 is kept for several hours until the reaction is completed(reaction is monitored by LC). The obtained product solution is used forthe third condensation step. II) To a solution of 0.030 mol ofintermediate prepared according to I) is added a solution of 5.59 g(0.0031 mol) m-phenylenediamine in 50 ml water. The reaction mixture isheated to 95° C. and a pH value of 8.5 is kept by addition of aqueous30% sodium hydroxide solution. The reaction is monitored by LC. After 3hours the reaction mixture is cooled to room temperature, a volume of950 ml solution is obtained. For isolation of the product, 237.5 g solidsodium chloride is added. The reaction mixture is stirred for another 12hours. The formed precipitate is filtered off and dried.

Yield: 42.2 g, UV_(vis) λ_(max) 536 nm.

2) The same dye can also be obtained by a twofold condensation of H-acidto cyanuric chloride, coupling of this intermediate with 2.6molequivalents of 1-aminonaphthalene-diazo (=30% excess) and subsequentcondensation with 1,3-phenylenediamine.

b) Synthesis of a Zinc phthalocyanine bis(monoazo) triazine dyeconjugate

A suspension of 800 mg Zinc phthalocyanine monosulfonyl chloride fromexample Ala in 20 ml ice water is treated with the bis(monoazo) triazinedye prepared above. The reaction and work-up is done according to thegeneral procedure 2.

The characterization was done by UV_(vis)-spectroscopy (λ 540 nm andλ_(max) 670 nm) and MS. The assignments of the detected structures aregiven in the following table.

Molecular weight (g/mol) structure 896

2007

816

1927

In the above structural formulas the sulfonation of the PC ringsindicates the isomeric structures, which are obtained. The aboverepresentation includes, therefore, all possible structural isomers.

EXAMPLE A3b Synthesis of a Zinc Phthalocyanine Bis(Monoazo) Triazine DyeConjugate

1.5 g Zinc phthalocyanine, 8.8 ml (14.9 g) chlorosulfuric acid and 1.0ml (1.7 g) of thionyl chloride are reacted as given in the generalprocedure 1a). The reaction mixture is given onto 25 g ice. Thetemperature is kept between 0-5° C. by addition of 140 g of ice. Theprecipitate is isolated as described in general procedure 1a) anddirectly further reacted. The crude Zinc phthalocyanine sulfonylchlorideis suspended in 50 ml of a mixture of ice and water. Within 5 minutes, asolution of an equimolar amount of bis(monoazo) triazine dye preparedabove is added. The reaction mixture is reacted and worked up bydialysis and dried by lyophilization according to general procedure 2).

The characterization is done by UV_(vis)-spectroscopy (λ 540 nm andλ_(max) 670 nm) and MS. The assignments of the detected structures aregiven in the following table:

Molecular weight (g/mol) structure 736

816

1191

1847

1927

2958

3038

EXAMPLE A4 Synthesis of a Zinc Phthalocyanine Bis(Monoazo) Triazine DyeConjugate

a) Synthesis of a Zinc phthalocyanine 4-tetrasulfonic acid derivative

15 g of 50 wt. % solution of 4-sulfophthalic acid (30.5 mmol), 2 g (9.11mmol) of Zinc acetate, 0.2 g (1.02 mmol) of ammonium molybdate and 5 mlof distilled water are stirred together until all of the solids aredissolved. 20 g (333 mmol) of urea are added to this solution and themixture is stirred until most of the urea was dissolved. This reactionmixture is poured into a reactor.

The reaction mixture is heated to 180° C. for one hour. The temperatureis then raised to 225° C. and maintained at that temperature for fivehours. After cooling to room temperature, the product is isolated andcharacterized by UV spectroscopy.

Yield: 11-12 g (crude).

The purity is checked by UV_(vis) spectroscopy, λ_(max): 669 nm, ε:25.000-35.000.

The crude sample is purified by methanol treatment and dialysis.

Yield: ˜2 g, λ_(max): 669 nm, ε: 120.000-139.000.

In contrast to the sulfonated Zinc phthalocyanines described in examples1-3, this phthalocyanine is exclusively sulfonated at the position 4 or5.

b) Synthesis of a Zinc phthalocyanine 4-tetrasulfonic acid mono sulfonylchloride derivative

The Zinc phthalocyanine 4-tetrasulfonic acid obtained according to theprocedure in example A4a) is transformed to the Zinc monosulfonylchloride according to the general procedure 1b.

c) Synthesis of a Zinc phthalocyanine monoazo dye conjugate

The wet cake of the Zinc phthalocyanine sulfonyl chloride of exampleA4b) is suspended in water and the pH is adjusted to 7 by adding 0.1NNaOH solution. This is then added to an aqueous solution of the monoazodescribed in example A3. The mixture is reacted, and worked-up accordingto the general procedure 2).

Application Examples

A bleached cotton fabric is treated with an aqueous solution of thecompounds described in the preparation examples A1-3. By this treatment,all fabrics are blue to violet colored. The fabrics are exposed in a wetstate for up to 120 min. to a tungsten lamp. The intensity of theblue/violet color of the fabric is continuously reduced upon exposure.

Washing Experiments

Bleached cotton is washed with a detergent containing photocatalystsfrom example A1-A3 for 15 min at 30° C. The amount of photocatalyst is0.04% by weight based on the weight of the detergent. The amount of dyegiven in Table 1, examples 1-3 is based on an initially equaldye-strength as measured by the absorption at 670 nm.

Detergent 40 gr/kg of fabric

Fabric to Liquor ratio 1:10

After washing one part of the fabrics they are exposed to tungsten lightfor two hours (light intensity, as measured with a Roline RO-1322Digital Lux meter at the position of the fabric, is within the range of17000 Lux). One part is dried in the dark. This washing cycle isrepeated four times. After the fourth cycle the amount of dye on thefabric dried in the dark and on the fabric dried under exposure isdetermined, using the Kubelka-Munck formula K/S. The amount of dye onthe fabric dried under exposure is given (Table 1) as percentage of theamount of dye that is determined on the fabric dried in the dark. Thelower the percentage the more dye is degraded during light exposure.

TABLE 1 Examples % dye remaining Example B1 (compound of example A1) 50%Example B2 (compound of example A2) 69% Example B3 (compound of exampleA3) 45% Example B4 (compound of example A3b) 54%

1. A phthalocyanine compound of formula (1)(PC)-L-(D)  (1) in which at least one mono-azo dyestuff is attachedthrough covalent bonding via a linking group L to a metal-containingphthalocyanine ring system wherein the metal (Me) is Zn, Ca, Mg, Na, K,Al, Si, Ti, Ge, Ga, Zr, In or Sn; PC is a metal-containingphthalocyanine ring system; D is a radical of a mono-azo dyestuff; and Lis a group

wherein R₂₀ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy or halogen; R₂₁ isindependently D, hydrogen, OH, Cl or F, with the proviso that at leastone is D; R₁₀₀ is C₁-C₈alkylene; * is the point of attachment of PC; and# is the point of attachment of the dyestuff.
 2. A compound according toclaim 1 of formula (1a)

in which PC is the phthalocyanine ring system, Me is Zn; Ca; Mg; Na; K;Si(IV)-(Z₁)₂; Ti(IV)-(Z₁)₂; Ge(IV)-(Z₁)₂; Ga(III)-Z₁; Zr(IV)-(Z₁)₂;In(III)-Z₁ or Sn(IV)-(Z₁)₂ Z₁ is an alkanolate ion; a hydroxyl ion;R₀COO⁻; ClO⁴⁻; BF₄ ⁻; PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻;citrate ion; tartrate ion or oxalate ion, wherein R₀ is hydrogen orunsubstituted C₁-C₁₈alkyl; r is 0; 1; 2; 3 or 4; r′ is 1; 2; 3 or 4;each Q₂ is independently of each other —SO; M⁺ or a group—(CH₂)_(m)—COO⁻M⁺; wherein M⁺ is H⁺, an alkali metal ion or an ammoniumion and m is 0 or a number from 1 to 12; each Q′ is independently fromeach other a moiety of formula -L-D wherein D is the radical of amono-azo dyestuff; and L is a group

wherein R₂₀ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy or halogen; R₂₁ isindependently D, hydrogen, OH, Cl or F, with the proviso that at leastone is D; R₁₀₀ is C₁-C₈alkylene; * is the point of attachment of PC; and# is the point of attachment of the dyestuff.
 3. A Compound according toclaim 1 of formula (2a)

wherein Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ ischloride, fluorine, bromine or hydroxyl; each Q₂ is independently fromeach other —SO₃ ⁻M⁺ or a group —(CH₂)_(m)—COO⁻M⁺; wherein M⁺ is H⁺, analkali metal ion or an ammonium ion and m is 0 or a number from 1 to 12;D is the radical of a dyestuff; L is a group

wherein R₂₁ is independently D, hydrogen, OH, Cl or F with the provisothat at least one is D; is the point of attachment of PC, # is the pointof attachment to D; r₂ is 0 or 1, r₃ is 0 or 1, and r₄ is 0 or
 1. 4. Acompound according to claim 1 wherein Me is Zn.
 5. A compound accordingto claim 1 wherein each D is independently from each other a dyestuffradical of formulae Xa, Xb, Xc or Xd

wherein # marks the bond to the linking group L, R_(α) is hydrogen;linear or branched, unsubstituted C₁-C₄-alkyl; linear or branchedC₁-C₄-alkyl, which is substituted by at least one substituent chosenfrom the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl;unsubstituted aryl or aryl, which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano, SO₃H,—NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl, Z₂, Z₃,Z₄, Z₅ and Z₆ are independently from each other hydrogen; linear orbranched, unsubstituted C₁-C₄alkyl; linear or branched C₁-C₄-alkyl,which is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy,C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched,unsubstituted C₁-C₄-alkoxy or linear or branched, C₁-C₄-alkoxy, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, Cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,phenyl, naphthyl and pyridyl; halogen; OH; SO₂CH₂CH₂SO₃H; NO₂; COOH;COOC₁-C₄alkyl; NH₂; NHC₁-C₄alkyl, wherein the alkyl group may besubstituted by at least one substituent chosen from the group consistingof OH, NH₂, C₁-C₄alkyl, CN and COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, whereinthe alkyl groups may independently of each other be substituted by atleast one substituent chosen from the group consisting of OH, NH₂,C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl, wherein the aryl issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₁alkyland C₁-C₄alkoxy; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl, G is a direct bond;COOC₁-C₄alkylene; unsubstituted arylene; arylene which is substituted byat least one substituent chosen from the group consisting of hydroxyl,cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy andC₁-C₄alkyl; unsubstituted C₁-C₄alkylene or C₁-C₄-alkylene which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy,C₁-C₄alkoxy and C₁-C₄alkyl; or —CO-arylene, n is 0; 1; 2 or 3, n′ is 0;1 or 2, and each M is independently from each other hydrogen; an alkalimetal ion or an ammonium ion.
 6. A compound according to claim 1 whereineach D is independently from each other a dyestuff radical of formulaeXIa, XIb, XIc or XId

wherein # marks the bond to the bridging group L, Z₂ is linear orbranched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl,which is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl,phenyl, naphthyl and pyridyl or OH, Z₃ is hydrogen; linear or branched,unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy,phenyl, naphthyl and pyridyl; linear or branched, unsubstitutedC₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substitutedby at least one substituent chosen from the group consisting ofhydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl,phenyl, naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein thealkyl group may be substituted by at least one substituent chosen fromthe group consisting of OH, NH₂, C₁-C₂alkyl, CN and COOH; NHCOC₁-C₂alkylor NHCOOC₁-C₂alkyl, Z₄ is hydrogen; linear or branched, unsubstitutedC₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by atleast one substituent chosen from the group consisting of hydroxyl,cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy orlinear or branched, C₁-C₂-alkoxy, which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano, SO₃H,—NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl andpyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl group may besubstituted by at least one substituent chosen from the group consistingof OH, NH₂, C₁-C₂alkyl, CN and COOH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl or linearor branched C₁-C₂-alkyl, which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano, SO₃H,—NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl andpyridyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene;arylene which is substituted by at least one substituent chosen from thegroup consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstitutedC₁-C₂alkylene or C₁-C₂alkylene which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano, NO₂,SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is0, 1; 2 or 3, n′ is 0, 1 or 2, and each M is independently from eachother hydrogen; Na⁺ or K⁺;

wherein # marks the bond to the bridging group L, Z₂ is linear orbranched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl,which is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl,phenyl, naphthyl and pyridyl or OH, Z₃ is hydrogen; linear or branched,unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which issubstituted, by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl,phenyl, naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein thealkyl group may be substituted by at least one substituent chosen fromthe group consisting of OH, NH₂, C₁-C₂alkyl, CN and COOH; NHCOC₁-C₂alkylor NHCOOC₁-C₂alkyl, Z₅ is hydrogen; linear or branched, unsubstitutedC₁-C₂-alkyl or linear or branched C₁-C₂-alkyl, which is substituted byat least one substituent chosen from the group consisting of hydroxyl,cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,naphthyl and pyridyl; G is a direct bond; COOC₁-C₂alkylene;unsubstituted arylene; arylene which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano, NO₂,SO₃H, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl;unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by atleast one substituent chosen from the group consisting of hydroxyl,cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy andC₁-C₂alkyl, n is 0, 1; 2 or 3, n′ is 0, 1 or 2, and each M isindependently from each other hydrogen; Na⁺ or K⁺;

wherein # marks the bond to the bridging group L, Z₂ is hydrogen; linearor branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl,which is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,phenyl, naphthyl and pyridyl; OH; NO₂, Z₃ is hydrogen; linear orbranched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl,which is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl,phenyl, naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein thealkyl group may be substituted by at least one substituent chosen fromthe group consisting of OH, NH₂, C₁-C₂alkyl, CN and COOH; NHCOC₁-C₂alkylor NHCOOC₁-C₂alkyl, Z₄ is hydrogen; linear or branched, unsubstitutedC₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by atleast one substituent chosen from the group consisting of hydroxyl,cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy orlinear or branched, C₁-C₂-alkoxy, which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano, SO₃H,—NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl andpyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl group may besubstituted by at least one substituent chosen from the group consistingof OH, NH₂, C₁-C₂alkyl, CN and COOH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear orbranched C₁-C₂-alkyl, which is substituted by at least one substituentchosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl;linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched,C₁-C₂-alkoxy, which is substituted by at least one substituent chosenfrom the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; NO₂, G is adirect bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene orC₁-C₂-alkylene which is substituted by at least one substituent chosenfrom the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 0, 1; 2 or 3, n′ is0, 1 or 2, and each M is independently from each other hydrogen; Na⁺ orK⁺;

wherein # marks the bond to the bridging group L, Z₃ is hydrogen; linearor branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl,which is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,phenyl, naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂, Z₄ is linear orbranched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl,which is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,phenyl, naphthyl and pyridyl; OH; SO₂CH₂CH₂SO₃H; or NO₂, Z₅ is hydrogen;linear or branched, unsubstituted C₁-C₂-alkyl; linear or branchedC₁-C₂-alkyl, which is substituted by at least one substituent chosenfrom the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear orbranched, unsubstituted C₁-C₂-alkoxy or linear or branched,C₁-C₂-alkoxy, which is substituted by at least one substituent chosenfrom the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; NO₂;NH₂; NHC₁-C₂alkyl, wherein the alkyl group may be substituted by atleast one substituent chosen from the group consisting of OH, NH₂,C₁-C₂alkyl, CN and COOH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, Z₆ is linearor branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl,which is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,phenyl, naphthyl and pyridyl; or NO₂, G is a direct bond;COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted byat least one substituent chosen from the group consisting of hydroxyl,cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy andC₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which issubstituted by at least one substituent chosen from the group consistingof hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,C₁-C₂alkoxy and C₁-C₂alkyl, n is 0, 1; 2 or 3, n′ is 0, 1 or 2, and eachM is independently from each other hydrogen; Na⁺ or K⁺
 7. A compoundaccording to claim 1 wherein each D is independently from each other acompound of formulae 10, 11, 12, 13 or 14

wherein # marks the bond to the bridging group L.
 8. A process forproducing compounds of formula (1a)

wherein X and X′ are leaving groups; Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ orTi(IV)-(Z₁)₂, wherein Z₁ is chloride, fluorine, bromine or hydroxyl;each Q is independently from each other —SO₃ ⁻M⁺ or a group—(CH₂)_(m)—COO⁻M⁺; wherein M⁺ is H⁺, an alkali metal ion or an theammonium ion and m is 0 or a number from 1 to 12; PC is thephthalocyanine ring system, D is the radical of a dyestuff; L is a group

wherein R₂₁ is independently D, hydrogen, OH, Cl or F with the provisothat at least one is D; * is the point of attachment of PC, # is thepoint of attachment to D; r is 0; 1; 2; 3 or 4; and r′ is 1; 2; 3 or 4.9. A process according to claim 8 wherein a sulfophthalic acid isreacted with a metal salt and urea in the presence of a molybdatecatalyst in a melt condensation.
 10. A shading composition in form of agranule comprising a) from 2 to 75% by weight (wt-%) of at least onephthalocyanine compound as defined in claim 1, based on the total weightof the granulate, b) from 10 to 95 wt-% of at least one furtheradditive, based on the total weight of the granulate, and c) from 0 to15 wt-% water, based on the total weight of the granulate.
 11. A shadingcomposition in liquid form comprising (a) 0.01-95 wt-% of aphthalocyanine compound of formula (1) as defined in claim 1, based onthe total weight of the liquid formulation, (b) 5-99.99 wt-%, based onthe total weight of the liquid formulation, of at least one solvent and(c) 0-10 wt-%, based on the total weight of the liquid formulation, ofat least one further additive.
 12. A compound of formula (A)

wherein M is H or Na.
 13. A compound of formula (A1)

wherein M is H or Na.
 14. A compound of formula (B1), (B2) or (B3)

wherein M is H or Na.